Selective oxidation of carbon monoxide and triphenylphosphine in carbonylphosphine complexes of rhodium (I)
The interactions of the complexes (RhCO(PPh/sub 3/)/sub 2/Cl), (RhCO(PPh/sub 3/)/sub 2/NO/sub 3/), (RhCO-(PPh/sub 3/)/sub 2/py)(ClO/sub 4/), and (RhCO(PPh/sub 3/)/sub 2/bipy)(NO/sub 3/) with oxygen donors, viz., trimethylamine oxide dihydrate, iodosobenzene, iodobenzene, and iodosobenzene diacetate, in acetonitrile, pyridine, and dimethylformamide have been investigated. The reaction of (RhCO(PPh/sub 3/)/sub 2/Cl) with an excess of trimethylamine oxide dihydrate in acetonitrile in air results in the selective oxidation of the coordinated carbon monoxide. In the decarbonylation product, triphenylphosphine is oxidized by atmospheric oxygen. Regeneration of the original complex (RhCO(PPh/sub 2/)/sub 2/Cl) with a low yield can be effected by adding ethanol or by bubbling CO through the reaction mixture in the presence of an excess of triphenylphosphine. The compound (Rh(PPh/sub 3/)/sub 3/Cl) has been obtained with a 45% yield by adding an excess of triphenylphosphine and isopropanol to the decarbonylation product in solution. The oxidation of (RhCO(PPh/sub 3/)/sub 2/ bipy)-(NO/sub 3/) by trimethylamine oxide dihydrate in pyridine in air results in the formation of the complex (Rh(bipy)py/sub 2/)/sup +/.
- Research Organization:
- A. A. Zhdanov, Leningrad State Univ. (USSR)
- OSTI ID:
- 7005497
- Journal Information:
- Sov. J. Coordinat. Chem.; (United States), Vol. 13:5; Other Information: Translated from Koordinatsionnaya Khimiya; 13: No. 5, 650-655(May 1987)
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CARBON MONOXIDE
OXIDATION
PHOSPHINES
RHODIUM COMPLEXES
REDOX POTENTIAL
ACETONITRILE
ACTIVATION ENERGY
AMIDES
BENZENE
BINDING ENERGY
ELECTRONS
HYDRATES
IODINATED AROMATIC HYDROCARBONS
ORGANIC SOLVENTS
PYRIDINES
SOLVENT PROPERTIES
VALENCE
AROMATICS
AZINES
CARBON COMPOUNDS
CARBON OXIDES
CHALCOGENIDES
CHEMICAL REACTIONS
COMPLEXES
ELEMENTARY PARTICLES
ENERGY
FERMIONS
HALOGENATED AROMATIC HYDROCARBONS
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
LEPTONS
NITRILES
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC IODINE COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PHOSPHORUS COMPOUNDS
SOLVENTS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties